CHEMICAL ADMIXTURES

Superplasticizers

Asst. Prof. Dr. Şevket Can BOSTANCI

Introduction
 Superplasticizers are chemicals, usually long-chain
molecules, which when added to concrete allow a large
reduction in water needed to achieve given workability or
alternatively impart extreme workability beyond that
achievable with normal water-reducing admixtures.

 The superplasticizers are a special category of water-reducing

agents in that they are formulated from materials that allow
much greater water reductions, or alternatively extreme
workability of concrete in which they are incorporated
Introduction
 Superplasticizers belong to a class of water reducers
chemically different from the normal water reducers and
capable of reducing water contents by about 30%.

 This is achieved without undesirable side effects such as

excessive air entrainment or set retardation.

 The admixtures belonging to high strength class are variously

known as superplasticizers, superfluidizers, superfluiddiers,
super water reducers, or high range water reducers.
Introduction
 They were first introduced and originally developed as the
basis for superplasticizers in the 1960s were sulfonated
naphthalene formaldehyde (SNF) and sulfonated melamine
formaldehyde (SMF) in Japan and Germany respectively in
Japan in the late 60’s and in Germany in early 70’s. In North
America they were used from 1974 which have found
increasing application world-wide over the intervening years.

 The advantages derived by the use of superplasticizers

include production of concrete having high workability for
easy placement, and production of high strength concrete
with normal workability but with a lower water content.
Introduction
The superplasticizers are broadly classified into four groups:
 Sulfonated melamine-formaldehyde condensate (SMF);
 Sulfonated naphthalene-formaldehyde condensate (SNF);
 Modified lignosulfonates (MLS);
 and others including sulfonic acid esters, polyacrylates,
polystyrene sulfonates, etc.
The chemistry of superplasticizers
 The three major types of raw materials used in superplasticizers,
SNF, SMF, and polyacrylates, which also illustrates the three
different types of polyacrylates.

 Minor amounts of other materials are often added such as

triethanolamine (to counteract retardation), tributyl phosphate (to
cut down excessive air entrainment) and hydroxycarboxylic acid
salts or lignosulfonates (to increase retardation).

 In addition proprietary superplasticizers can be blends of two of

the main ingredients.
The chemistry of superplasticizers
Sulfonated naphthalene formaldehyde
 This raw material was one of the first materials referred to in the
literature as a water-reducing agent yet only since 1970 has it
found extensive application in admixture formulations.

 The material is produced from naphthalene by oleum or sulfur

trioxide sulfonation under conditions conducive to the formation
of the ß sulfonate. Subsequent reaction with formaldehyde leads to
polymerization and the sulfonic acid is neutralized with sodium
hydroxide or lime.

 Commercial products vary from 25 to 45% w/w solids contents

and addition levels required to produce concrete of almost self-
compacting properties would be 1.0–3.0% by weight of cement.
 Sulfonated melamine formaldehyde
 This type of chemical product was originally developed in the
1950s as a dispersant for a wide variety of industries, but it was
not until some 10 years later that the possibilities for its use in
concrete were recognized.

 This material is normally used alone or in combination with SNF.

When used alone it is typified by having minimal effect on air
entrainment or setting time. Hydroxycarboxylic acids have been
incorporated into some formulations in order to cut down slump
loss.
Polyacrylates
 The various types of polyacrylate polymers are manufactured
from the relevant monomers by a free radical mechanism
using peroxide initiators and can be ‘block’ or ‘random’
polymers depending on the degree of pre-polymerization of
the monomers used.
 Effects of superplasticizers on the
properties of concrete
The properties of concrete can be considered in terms of:

 The initial plastic state of the fresh concrete when

properties such as the workability as measured by slump or
flow table test or air content can be determined by the
relevant standard method.

 The later plastic state when the concrete may be

transported, handled and placed; changes in air content and
workability may occur and setting time may be a factor in the
finishing operation.
 Effects of superplasticizers on the
properties of concrete
 The hardened state at a relatively early age (usually 28
days) where mechanical properties are determined as a basis
of structural requirements.

 The later hardened state during its in place life when the
concrete should fulfill its structural or aesthetic role without
deterioration under the service conditions.
 The effects of superplasticizers on the
properties of plastic concrete
Air entrainment
Different types of superplasticizers alter the air content of fresh
concrete in varying degrees and the effect is also dependent on the
way the superplasticizer is used. In general, the following
observations are noted:

 1. When the superplasticizer is used to produce highly workable

concrete, more air will be entrained than a control concrete. This
is particularly true of SNF and polyacrylate types (where air-
detraining agents are sometimes intentionally added into the
formulations) and less so with the SMF type.
 The effects of superplasticizers on the
properties of plastic concrete
 2. When superplasticizers are used to reduce the water-cement
ratio, normally any increase in air content will be minimal,
especially in high-cement-content mixes. When it is a requirement
to intentionally air-entrain such mixes, the dosage required to
obtain a given air content is often considerably increased,
presumably because of the reduced aqueous medium in the
concrete.

 3. The stability of entrained air in superplasticized concrete has

been studied in the laboratory and the SMF type appears to lose
air more rapidly than SNF. Full-scale trials carried out with a
polyacrylate type of superplasticizer on ready-mixed concrete
indicated that the particular type of material evaluated produced a
very stable air void system.
 The effects of superplasticizers on the
properties of plastic concrete
Workability
 Superplasticizers cause dramatic increases in workability as
measured by slump or flow table spread, or alternatively
allow very large decreases in water-cement ratios to be made
while maintaining workability.

 A major drawback to the practical use of superplasticizers to

produce highly workable, almost self-compacting concrete,
has been the short duration of the extreme workability, often
only 30–40 min.
 The effects of superplasticizers on the
properties of plastic concrete
Setting time
 The effect that superplasticizers have on the setting times of
concrete depends on a number of factors including the type
of superplasticizer, cement composition, and particularly
whether there is a simple addition of the admixture to the
concrete or if a reduction in water-cement ratio is made.
 The effects of superplasticizers on the
properties of plastic concrete
Setting time
In general it can be stated that:
 1. With a direct addition of superplasticizer to obtain highly
workable concrete, initial and final setting times are invariably
increased in the order SMF < SNF < polyacrylates. At normal
dosages this increase rarely exceeds two hours for materials that
are not intentionally formulated to retard.

 2. When the water-cement ratio is reduced to give a similar slump

to a control mix, the setting time is normally very similar to the
control; perhaps a small decrease in the case of SMF and SNF and
a slight increase in the case of polyacrylate-based materials,
normally no greater than one hour either way.
The effects of superplasticizers on the
properties of hardened concrete
 The major physical attributes of concrete that make it a
construction material of choice are its high compressive
strength and stiffness and its ability to protect reinforcing
steel. It is also important that these properties are maintained
during the service life and that any addition, such as
superplasticizers, have no adverse effects on these attributes.
 The effects of superplasticizers on the
properties of hardened concrete
Compressive strength
 In general, superplasticizers will not have an adverse effect on
strength, or strength development of concrete when added to
produce highly workable concrete without reducing the water
content. In fact several studies have indicated that an increase in
strength may occur, and in some cases this can be substantial for an
SMF-based material.

 The increases in strength by using superplasticizers to reduce the

water-cement ratio appear to be consistent over several cement
and superplasticizer types and continues beyond the 28-day result,
which also indicates how flexural strength and modulus are
similarly affected
The effects of superplasticizers on the
properties of hardened concrete
Shrinkage and creep
 Most of the studies in this area have indicated that
superplasticized concrete has shrinkage and creep
characteristics similar to plain concrete.
 The effects of superplasticizers on the
properties of hardened concrete
Freeze-thaw durability
In the early days of the use of superplasticized concrete, some
concerns were aired regarding the resistance of air-entrained
concrete containing superplasticizers to freeze-thaw cycling.
However, more recent research has indicated the following:

 1. In air-entrained superplasticized concrete, the commonly

accepted minimum value of the spacing factor of the air void
system (0.2 mm) to provide adequate freeze-thaw protection is
usually exceeded.

 2. Despite the fact that the minimum spacing factor is exceeded,

the concrete freeze-thaw resistance of the concrete does not
appear to be adversely affected.
Sulfate resistance
 Research into the susceptibility of superplasticized concrete
to sulfate attack has concluded that there is no significant
difference between plain concrete and the admixture-
containing concrete presents some data for concretes
containing an SNF superplasticizer exposed to a 3%
magnesium sulfate solution.
Main applications
 Congested reinforcing
Superplasticizers used to produce high workability enable
concrete to be placed more easily in congested and inaccessible
sections.

 Floor Slabs
Flowing concrete enables floor and pavement slabs which are
not laid to falls to be placed quickly, with little or no vibration
and with very low labour content.
Main applications
 Improved quality
By a combination of water-reduction and improved workability
superplasticizers can be used to improve the quality and
durability of concrete.

 Early demoulding
By using superplasticizers to reduce water content and lower
the w/c ratio, it is possible to increase early strength and allow
earlier demoulding. This is an alternative to using an accelerator
or heat curing.
Formwork (Precaution)
 The increased fluidity of flowing concrete means that
additional pressures are brought to bear on formwork.

 Formwork should be designed to resist full hydrostatic

pressure.

 Any initial tendency of flowing concrete to leak through gaps

in formwork normally ceases within a matter of minutes
References
 Dodson, V. H. (1990) Concrete Admixtures. 1st Ed., Springer
Science and Business Media, NewYork.

 Proceeding of the International RILEM Symposium. (1990)

Admixtures for Concrete. Edited by E. Vasquez., 1st Ed.,
Chapman and Hall, UK.

 Ramachandran, V.S. (1995) Concrete Admixtures Handbook. 2nd

Ed., Noyes Publication, New Jersey, USA.